Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published December 26, 2011 | Accepted Version + Supplemental Material
Journal Article Open

Thermally Stable, Latent Olefin Metathesis Catalysts


Highly thermally stable N-aryl, N-alkyl N-heterocyclic carbene (NHC) ruthenium catalysts were designed and synthesized for latent olefin metathesis. These catalysts showed excellent latent behavior toward metathesis reactions, whereby the complexes were inactive at ambient temperature and initiated at elevated temperatures, a challenging property to achieve with second-generation catalysts. A sterically hindered N-tert-butyl substituent on the NHC ligand of the ruthenium complex was found to induce latent behavior toward cross-metathesis reactions, and exchange of the chloride ligands for iodide ligands was necessary to attain latent behavior during ring-opening metathesis polymerization (ROMP). Iodide-based catalysts showed no reactivity toward ROMP of norbornene-derived monomers at 25 °C and upon heating to 85 °C gave complete conversion of monomer to polymer in less than 2 h. All of the complexes were very stable to air, moisture, and elevated temperatures up to at least 90 °C and exhibited a long catalyst lifetime in solution at elevated temperatures.

Additional Information

© 2011 American Chemical Society. Received: September 29, 2011. Publication Date (Web): November 18, 2011. This research was supported by the National Science Foundation through a Graduate Fellowship to R.M.T. and by the Department of Defense through a Graduate Fellowship to B.K.K. A.F. thanks the Swiss National Science Foundation for a postdoctoral fellowship. We thank Dr. Rosemary Conrad for the synthesis of monomer 6. We thank the NSF and NIH for providing funding and Materia for gifts of catalyst precursors.

Attached Files

Accepted Version - nihms339914.pdf

Supplemental Material - om200911e_si_001.pdf

Supplemental Material - om200911e_si_002.cif

Supplemental Material - om200911e_si_003.cif

Supplemental Material - om200911e_si_004.cif


Files (884.6 kB)
Name Size Download all
5.1 kB Download
5.0 kB Download
407.4 kB Preview Download
462.0 kB Preview Download
5.1 kB Download

Additional details

August 19, 2023
October 24, 2023